Select elastomeric blends and their use in articles

ABSTRACT

The present invention relates to select elastomeric blends including at least one halogenated random copolymer. In particular, the present invention relates to compositions including at least one halogenated random copolymer of isobutylene and methylstyrene, preferably para-methylstyrene; wherein the at least one halogenated random copolymer includes at least 9.0 wt % methylstyrene, preferably para-methylstyrene, based upon the weight of the at least one halogenated random copolymer; and at least one general purpose rubber. The invention also relates to articles made from these compositions and processes for making the same.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a 371 National Stage Application of InternationalApplication No. PCT/US2005/035052, filed Sep. 30, 2005, which claimsbenefit of U.S. Provisional Application Ser. No. 60/639,939, filed Dec.29, 2004, the disclosures of which are herein incorporated by referencein their entireties.

FIELD OF THE INVENTION

The present invention relates to select elastomeric blends including atleast one halogenated random copolymer. In particular, the presentinvention relates to compositions including at least one halogenatedrandom copolymer of isobutylene and methylstyrene, preferablypara-methylstyrene; wherein the at least one halogenated randomcopolymer includes at least 9.0 wt % methylstyrene, preferablypara-methylstyrene, based upon the weight of the at least onehalogenated random copolymer; and at least one general purpose rubber.The invention also relates to articles made from these compositions andprocesses for making the same.

BACKGROUND

In the tire industry, manufacturers of tires and tire components haveendless choices when fabricating such items. For example, the selectionof ingredients for the commercial formulations of tires and tirecomponents depends upon the balance of properties desired and the enduse. In particular, when fabricating that portion of the tire reliedupon for air impermeability such as the tire innerliner, manufacturershave applied a myriad approaches including the widespread use of “butyl”rubbers or elastomers in various embodiments. Butyl rubbers, generally,copolymers of isobutylene and isoprene, optionally halogenated, havewidespread application due to their ability to impart desirable airimpermeability properties for the tire. For example, due to economicadvantages and processing benefits, blends of butyl rubbers with otherrubbers such as natural rubbers have been useful.

However, such blends have their limitations. Thus, the tire industrycontinually seeks improvements to past applications. For example,Exxpro™ elastomers (ExxonMobil Chemical Company, Houston, Tex.),generally, halogenated random copolymers of isobutylene andpara-methylstyrene, have been of particular interest due to theirimprovements over butyl rubbers. Similarly, as with butyl rubbers, dueto economics and processing goals, producing a tire or tire componentsfrom 100% Exxpro™ elastomers is not the tire industry's idealapplication. Therefore, in many cases, a blend of Exxpro™ elastomerswith secondary elastomers or other polymers affords a compound having adesirable balance of properties achieved through suitable processingwindows. See, e.g., U.S. Pat. Nos. 6,293,327, and 5,386,864, U.S. PatentApplication Publication No. 2002/151636, JP 2003170438, and JP2003192854 (applying various approaches of blends of commercial EXXPRO™elastomers with other polymers).

Other background references include U.S. Pat. Nos. 5,063,268, 5,391,625,6,051,653, and 6,624,220, WO 1992/02582, WO 1992/03302, WO 2004/058825,EP 1 331 107 A, and EP 0 922 732 A.

However, due to the rigorous demands of tires and the tire industry'srelentless pursuit of a better tire and/or a better process to producethe tire or its respective components, improvements to these blends arealso desired. For example, commercial Exxpro™ elastomers, generallyhaving about 5 wt % or about 7 wt % para-methylstyrene based upon theweight of the random copolymer, used alone or in combination with otherpolymers in blends, still necessitate improvements to the balances ofproperties for the tire or tire component and/or the process to producethe tire or tire components. Thus, the problem of improvingprocessability of elastomeric compositions useful for tire articleswhile maintaining or improving the air impermeability and/or otherproperties of those compositions still remains.

SUMMARY OF THE INVENTION

In an embodiment, the invention provides for a composition comprising:at least one halogenated random copolymer of isobutylene andmethylstyrene; wherein the at least one halogenated random copolymercomprises at least 9.0 wt % methylstyrene, preferablypara-methylstyrene, based upon the weight of the at least onehalogenated random copolymer; and at least one general purpose rubber.

In an embodiment, the at least one halogenated random copolymer maycomprise at least 9.5 wt % methylstyrene, preferably para-methylstyrene,based upon the weight of the at least one halogenated random copolymer.

In an embodiment, the at least one halogenated random copolymer maycomprise at least 10.0 wt % methylstyrene, preferablypara-methylstyrene, based upon the weight of the at least onehalogenated random copolymer.

In an embodiment, the at least one halogenated random copolymer maycomprise at least 11.0 wt % methylstyrene, preferablypara-methylstyrene, based upon the weight of the at least onehalogenated random copolymer.

In an embodiment, the at least one halogenated random copolymer maycomprise at least 12.0 wt % methylstyrene, preferablypara-methylstyrene, based upon the weight of the at least onehalogenated random copolymer.

In an embodiment, the at least one halogenated random copolymer maycomprise at least 13.0 wt % methylstyrene, preferablypara-methylstyrene, based upon the weight of the at least onehalogenated random copolymer.

In any of the previous embodiments, the composition may comprise from 70phr to 97 phr of the at least halogenated one random copolymer and from30 phr to 3 phr of the at least one general purpose rubber.

In any of the previous embodiments, the composition may comprise from 75phr to 97 phr of the at least halogenated one random copolymer and from25 phr to 3 phr of the at least one general purpose rubber.

In any of the previous embodiments, the composition may comprise from 80phr to 97 phr of the at least halogenated one random copolymer and from20 phr to 3 phr of the at least one general purpose rubber.

In any of the previous embodiments, the composition may comprise from 85phr to 97 phr of the at least halogenated one random copolymer and from15 phr to 3 phr of the at least one general purpose rubber.

In any of the previous embodiments, the composition may comprise from 90phr to 97 phr of the at least halogenated one random copolymer and from10 phr to 3 phr of the at least one general purpose rubber.

In any of the previous embodiments, the at least one general purposerubber may comprise natural rubbers (NR), polyisoprene rubber (IR),poly(styrene-co-butadiene) rubber (SBR), polybutadiene rubber (BR),poly(isoprene-co-butadiene) rubber (IBR), styrene-isoprene-butadienerubber (SIBR), ethylene-propylene rubber (EPM), ethylene-propylene-dienerubber (EPDM), or mixtures thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a comparison of an inventive blend, one embodiment of theinvention, as compared to blends commonly practiced in industry in termsof Inflation Pressure Retention (IPR).

FIG. 2 shows a comparison of an inventive blend, one embodiment of theinvention, as compared to blends commonly practiced in industry in termsof Tire Durability.

FIG. 3 shows a comparison of an inventive blend, one embodiment of theinvention, as compared to blends commonly practiced in industry in termsof Intracarcass Pressure (ICP).

DETAILED DESCRIPTION OF THE INVENTION

Various specific embodiments, versions and examples of the inventionwill now be described, including preferred embodiments and definitionsthat are adopted herein for purposes of understanding the claimedinvention. For determining infringement, the scope of the “invention”will refer to any one or more of the appended claims, including theirequivalents, and elements or limitations that are equivalent to thosethat are recited.

As used herein, the new numbering scheme for the Periodic Table Groupsis used as set forth in CHEMICAL AND ENGINEERING NEWS, 63(5), p 27(1985).

As used herein, a polymer may be used to refer to homopolymers,copolymers, interpolymers, terpolymers, etc. Likewise, a copolymer mayrefer to a polymer comprising at least two monomers, optionally withother monomers.

As used herein, when a polymer is referred to as comprising a monomer,the monomer is present in the polymer in the polymerized form of themonomer or in the derivative form the monomer. Likewise, when catalystcomponents are described as comprising neutral stable forms of thecomponents, it is well understood by one skilled in the art, that theionic form of the component is the form that reacts with the monomers toproduce polymers.

As used herein, elastomer or elastomeric composition refers to anypolymer or composition of polymers (such as blends of polymers)consistent with the ASTM D1566 definition. Elastomer includes mixedblends of polymers such as melt mixing and/or reactor blends ofpolymers. The terms may be used interchangeably with the term“rubber(s).”

As used herein, phr is parts per hundred rubber, and is a measure commonin the art wherein components of a composition are measured relative toa major elastomer component, based upon 100 parts by weight of theelastomer(s) or rubber(s).

As used herein, isobutylene based elastomer or polymer refers toelastomers or polymers comprising at least 70 mol % repeat units fromisobutylene.

As used herein, isoolefin refers to any olefin monomer having at leastone carbon having two substitutions on that carbon.

As used herein, multiolefin refers to any monomer having two or moredouble bonds, for example, a multiolefin may be any monomer comprisingtwo conjugated double bonds such as a conjugated diene such as isoprene.

As used herein, hydrocarbon refers to molecules or segments of moleculescontaining primarily hydrogen and carbon atoms. In some embodiments,hydrocarbon also includes halogenated versions of hydrocarbons andversions containing heteroatoms as discussed in more detail below.

Embodiments of the present invention include an elastomeric compositioncomprising at least one random copolymer comprising a C₄ to C₇isomonoolefin. The at least one random copolymer may be halogenatedwith, for example, bromine or chlorine. In an embodiment, the at leastone random copolymer is poly(isobutylene-co-p-alkylstyrene) comprisingat least 10 wt % p-alkylstyrene, such as p-methylstyrene, based upon thetotal weight of the at least one random copolymer.

The elastomeric composition may also include a secondary elastomer. Thesecondary elastomer may be selected from “a general purpose rubber” suchas natural rubber, butadiene rubber, and styrene-butadiene rubber, andmixtures thereof. The composition may also include at least onethermoplastic resin, at least one filler, and/or modified layered fillersuch as an organically modified exfoliated clay.

Elastomers

Elastomeric compositions of the present invention include at least onerandom copolymer comprising a C₄ to C₇ isomonoolefins, such asisobutylene and an alkylstyrene comonomer, such as para-methylstyrene,containing at least 80%, more alternatively at least 90% by weight ofthe para-isomer and optionally include functionalized interpolymerswherein at least one or more of the alkyl substituents groups present inthe styrene monomer units contain benzylic halogen or some otherfunctional group. In another embodiment, the polymer may be a randomelastomeric copolymer of ethylene or a C₃ to C₆ α-olefin and analkylstyrene comonomer, such as para-methylstyrene containing at least80%, alternatively at least 90% by weight of the para-isomer andoptionally include functionalized interpolymers wherein at least one ormore of the alkyl substituents groups present in the styrene monomerunits contain benzylic halogen or some other functional group. Exemplarymaterials may be characterized as polymers containing the followingmonomer units randomly spaced along the polymer chain:

wherein R and R¹ are independently hydrogen, lower alkyl, such as a C₁to C₇ alkyl and primary or secondary alkyl halides and X is a functionalgroup such as halogen. In an embodiment, R and R¹ are each hydrogen. Upto 60 mol % of the para-substituted styrene present in the randompolymer structure may be the functionalized structure (2) above in oneembodiment, and in another embodiment from 0.1 to 5 mol %. In yetanother embodiment, the amount of functionalized structure (2) is from0.2 to 3 mol %.

The functional group X may be halogen or some other functional groupwhich may be incorporated by nucleophilic substitution of benzylichalogen with other groups such as carboxylic acids; carboxy salts;carboxy esters, amides and imides; hydroxy; alkoxide; phenoxide;thiolate; thioether; xanthate; cyanide; cyanate; amino and mixturesthereof. These functionalized isomonoolefin copolymers, their method ofpreparation, methods of functionalization, and cure are moreparticularly disclosed in U.S. Pat. No. 5,162,445.

In an embodiment, the elastomer comprises random polymers of isobutyleneand para-methylstyrene containing from 0.5 to 20 mol %para-methylstyrene wherein up to 60 mol % of the methyl substituentgroups present on the benzyl ring contain a bromine or chlorine atom,such as a bromine atom (para-(bromomethylstyrene)), as well as acid orester functionalized versions thereof.

In another embodiment, the functionality is selected such that it canreact or form polar bonds with functional groups present in the matrixpolymer, for example, acid, amino or hydroxyl functional groups, whenthe polymer components are mixed at high temperatures.

In certain embodiments, the random copolymers have a substantiallyhomogeneous compositional distribution such that at least 95% by weightof the polymer has a para-alkylstyrene content within 10% of the averagepara-alkylstyrene content of the polymer. Exemplary polymers arecharacterized by a narrow molecular weight distribution (Mw/Mn) of lessthan 5, alternatively less than 2.5, an exemplary viscosity averagemolecular weight in the range of from 200,000 up to 2,000,000 and anexemplary number average molecular weight in the range of from 25,000 to750,000 as determined by gel permeation chromatography.

The elastomer such as the random copolymer discussed above may beprepared by a slurry polymerization, typically in a diluent comprising ahalogenated hydrocarbon(s) such as a chlorinated hydrocarbon and/or afluorinated hydrocarbon including mixtures thereof, (see e.g., WO2004/058828, WO 2004/058827, WO 2004/058835, WO 2004/058836, WO2004/058825, WO 2004/067577, and WO 2004/058829), of the monomer mixtureusing a Lewis acid catalyst, followed by halogenation, preferablybromination, in solution in the presence of halogen and a radicalinitiator such as heat and/or light and/or a chemical initiator and,optionally, followed by electrophilic substitution of bromine with adifferent functional moiety.

In an embodiment, brominated poly(isobutylene-co-p-methylstyrene)“BIMSM” polymers generally contain from 0.1 to 5% mole ofbromomethylstyrene groups relative to the total amount of monomerderived units in the copolymer. In another embodiment, the amount ofbromomethyl groups is from 0.2 to 3.0 mol %, and from 0.3 to 2.8 mol %in yet another embodiment, and from 0.4 to 2.5 mol % in yet anotherembodiment, and from 0.3 to 2.0 in yet another embodiment, wherein adesirable range may be any combination of any upper limit with any lowerlimit. Expressed another way, exemplary copolymers contain from 0.2 to10 wt % of bromine, based on the weight of the polymer, from 0.4 to 6 wt% bromine in another embodiment, and from 0.6 to 5.6 wt % in anotherembodiment, are substantially free of ring halogen or halogen in thepolymer backbone chain. In one embodiment, the random polymer is acopolymer of C₄ to C₇ isoolefin derived units (or isomonoolefin),para-methylstyrene derived units and para-(halomethylstyrene) derivedunits, wherein the para-(halomethylstyrene) units are present in thepolymer from 0.4 to 3.0 mol % based on the total number ofpara-methylstyrene, and wherein the para-methylstyrene derived units arepresent from 3 to 15 wt % based on the total weight of the polymer inone embodiment, and from 4 to 10 wt % in another embodiment. In anotherembodiment, the para-(halomethylstyrene) is para-(bromomethylstyrene).

In embodiments directed to blends, the at least one random copolymer asdescribed above may be combined with a “general purpose rubber.”

A general purpose rubber, often referred to as a commodity rubber, maybe any rubber that usually provides high strength and good abrasionalong with low hysteresis and high resilience. These elastomers requireantidegradants in the mixed compound because they generally have poorresistance to both heat and ozone. They are often easily recognized inthe market because of their low selling prices relative to specialtyelastomers and their big volumes of usage as described by School inRUBBER TECHNOLOGY COMPOUNDING AND TESTING FOR PERFORMANCE, p 125 (Dick,ed., Hanser, 2001).

Examples of general purpose rubbers include natural rubbers (NR),polyisoprene rubber (IR), poly(styrene-co-butadiene) rubber (SBR),polybutadiene rubber (BR), poly(isoprene-co-butadiene) rubber (IBR), andstyrene-isoprene-butadiene rubber (SIBR), and mixtures thereof.Ethylene-propylene rubber (EPM) and ethylene-propylene-diene rubber(EPDM), and their mixtures, often are also referred to as generalpurpose elastomers.

In another embodiment, the composition may also comprise a naturalrubber. Natural rubbers are described in detail by Subramaniam in RUBBERTECHNOLOGY, P 179-208 (Morton, ed., Chapman & Hall, 1995). Desirableembodiments of the natural rubbers of the present invention are selectedfrom Malaysian rubber such as SMR CV, SMR 5, SMR 10, SMR 20, and SMR 50and mixtures thereof, wherein the natural rubbers have a Mooneyviscosity at 100° C. (ML 1+4) of from 30 to 120, more preferably from 40to 65. The Mooney viscosity test referred to herein is in accordancewith ASTM D-1646.

In another embodiment, the composition may also comprise a polybutadiene(BR) rubber. The Mooney viscosity of the polybutadiene rubber asmeasured at 100° C. (ML 1+4) may range from 35 to 70, from 40 to about65 in another embodiment, and from 45 to 60 in yet another embodiment. Acommercial example of these synthetic rubbers useful in the presentinvention are BUDENE™ 1207 or BR 1207 (Goodyear Chemical Company, Akron,Ohio). An example is high cis-polybutadiene (cis-BR). By“cis-polybutadiene” or “high cis-polybutadiene”, it is meant that1,4-cis polybutadiene is used, wherein the amount of cis component is atleast 95%. A particular example of high cis-polybutadiene commercialproducts used in the composition BUDENE™ 1207.

In another embodiment, the composition may also comprise a polyisoprene(IR) rubber. The Mooney viscosity of the polyisoprene rubber as measuredat 100° C. (ML 1+4) may range from 35 to 70, from 40 to about 65 inanother embodiment, and from 45 to 60 in yet another embodiment. Acommercial example of these synthetic rubbers useful in the presentinvention is NATSYN™ 2200 (Goodyear Chemical Company, Akron, Ohio).

In another embodiment, the composition may also comprise rubbers ofethylene and propylene derived units such as EPM and EPDM as suitableadditional rubbers. Examples of suitable comonomers in making EPDM areethylidene norbornene, 1,4-hexadiene, dicyclopentadiene, as well asothers. These rubbers are described in RUBBER TECHNOLOGY, p 260-283(1995). A suitable ethylene-propylene rubber is commercially availableas VISTALON™ (ExxonMobil Chemical Company, Houston, Tex.).

In another embodiment, the composition may comprise a so calledsemi-crystalline copolymer (“SCC”). Semi-crystalline copolymers aredescribed in WO 00/69966. Generally, the SCC is a copolymer of ethyleneor propylene derived units and α-olefin derived units, the α-olefinhaving from 4 to 16 carbon atoms in one embodiment, and in anotherembodiment the SCC is a copolymer of ethylene derived units and α-olefinderived units, the α-olefin having from 4 to 10 carbon atoms, whereinthe SCC has some degree of crystallinity. In a further embodiment, theSCC is a copolymer of 1-butene derived units and another α-olefinderived unit, the other α-olefin having from 5 to 16 carbon atoms,wherein the SCC also has some degree of crystallinity. The SCC can alsobe a copolymer of ethylene and styrene.

The elastomer may be present in the composition in a range from up to 90phr in one embodiment, from up to 50 phr in another embodiment, from upto 40 phr in another embodiment, and from up to 30 phr in yet anotherembodiment. In yet another embodiment, the elastomer may be present fromat least 2 phr, and from at least 5 phr in another embodiment, and fromat least 5 phr in yet another embodiment, and from at least 10 phr inyet another embodiment. A desirable embodiment may include anycombination of any upper phr limit and any lower phr limit.

For example, the elastomer, either individually or as a blend of rubbersmay be present in the composition from 5 phr to 90 phr in oneembodiment, and from 10 to 80 phr in another embodiment, and from 30 to70 phr in yet another embodiment, and from 40 to 60 phr in yet anotherembodiment, and from 5 to 50 phr in yet another embodiment, and from 5to 40 phr in yet another embodiment, and from 20 to 60 phr in yetanother embodiment, and from 20 to 50 phr in yet another embodiment, thechosen embodiment depending upon the desired end use application of thecomposition.

Thermoplastic Resin

The compositions of the invention may optionally include a thermoplasticresin. Thermoplastic resins suitable for practice of the presentinvention may be used singly or in combination and are resins containingnitrogen, oxygen, halogen, sulfur or other groups capable of interactingwith aromatic functional groups such as halogen or acidic groups. Theresins are present from 30 to 90 wt % in one embodiment, and from 40 to80 wt % in another embodiment, and from 50 to 70 wt % in yet anotherembodiment. In yet another embodiment, the resin is present at a levelof greater than 40 wt %, and greater than 60 wt % in another embodiment.

Suitable thermoplastic resins include resins selected from the groupconsisting or polyamides, polyimides, polycarbonates, polyesters,polysulfones, polylactones, polyacetals, acrylonitrile-butadiene-styreneresins (ABS), polyphenyleneoxide (PPO), polyphenylene sulfide (PPS),polystyrene, styrene-acrylonitrile resins (SAN), styrene maleicanhydride resins (SMA), aromatic polyketones (PEEK, PED, and PEKK) andmixtures thereof.

Suitable thermoplastic polyamides (nylons) comprise crystalline orresinous, high molecular weight solid polymers including copolymers andterpolymers having recurring amide units within the polymer chain.Polyamides may be prepared by polymerization of one or more epsilonlactams such as caprolactam, pyrrolidione, lauryllactam andaminoundecanoic lactam, or amino acid, or by condensation of dibasicacids and diamines. Both fiber-forming and molding grade nylons aresuitable. Examples of such polyamides are polycaprolactam (nylon-6),polylauryllactam (nylon-12), polyhexamethyleneadipamide (nylon-6,6)polyhexamethyleneazelamide (nylon-6,9), polyhexamethylenesebacamide(nylon-6,10), polyhexamethyleneisophthalamide (nylon-6, IP) and thecondensation product of 11-amino-undecanoic acid (nylon-11). Additionalexamples of satisfactory polyamides (especially those having a softeningpoint below 275° C.) are described in 16 ENCYCLOPEDIA OF CHEMICALTECHNOLOGY, P 1-105 (John Wiley & Sons 1968), CONCISE ENCYCLOPEDIA OFPOLYMER SCIENCE AND TECHNOLOGY, P 748-761 (John Wiley & Sons, 1990), and10 ENCYCLOPEDIA OF POLYMER SCIENCE AND TECHNOLOGY, P 392-414 (John Wiley& Sons 1969). Commercially available thermoplastic polyamides may beadvantageously used in the practice of this invention, with linearcrystalline polyamides having a softening point or melting point between160 and 260° C. being preferred.

Suitable thermoplastic polyesters which may be employed include thepolymer reaction products of one or a mixture of aliphatic or aromaticpolycarboxylic acids esters of anhydrides and one or a mixture of diols.Examples of satisfactory polyesters include poly(trans-1,4-cyclohexyleneC₂₋₆ alkane dicarboxylates such as poly(trans-1,4-cyclohexylenesuccinate) and poly(trans-1,4-cyclohexylene adipate); poly(cis ortrans-1,4-cyclohexanedimethylene) alkanedicarboxylates such aspoly(cis-1,4-cyclohexanedimethylene) oxlate andpoly-(cis-1,4-cyclohexanedimethylene) succinate, poly(C₂₋₄ alkyleneterephthalates) such as polyethyleneterephthalate andpolytetramethylene-terephthalate, poly(C₂₋₄ alkylene isophthalates suchas polyethyleneisophthalate and polytetramethylene-isophthalate and likematerials. Preferred polyesters are derived from aromatic dicarboxylicacids such as naphthalenic or phthalic acids and C₂ to C₄ diols, such aspolyethylene terephthalate and polybutylene terephthalate. Preferredpolyesters will have a melting point in the range of 160° C. to 260° C.

Poly(phenylene ether) (PPE) thermoplastic resins which may be used inaccordance with this invention are well known, commercially availablematerials produced by the oxidative coupling polymerization of alkylsubstituted phenols. They are generally linear, amorphous polymershaving a glass transition temperature in the range of 190° C. to 235° C.These polymers, their method of preparation and compositions withpolystyrene are further described in U.S. Pat. No. 3,383,435.

Other thermoplastic resins which may be used include the polycarbonateanalogs of the polyesters described above such as segmented poly (etherco-phthalates); polycaprolactone polymers; styrene resins such ascopolymers of styrene with less than 50 mol % of acrylonitrile (SAN) andresinous copolymers of styrene, acrylonitrile and butadiene (ABS);sulfone polymers such as polyphenyl sulfone; copolymers and homopolymersof ethylene and C₂ to C₈ α-olefins, in one embodiment a homopolymer ofpropylene derived units, and in another embodiment a random copolymer orblock copolymer of ethylene derived units and propylene derived units,and like thermoplastic resins as are known in the art.

Fillers

The elastomeric composition may have one or more filler components. Forease of reference, materials described herein and their equivalents willbe referred to as filler(s). Examples include but are not limited tocalcium carbonate, clay, mica, silica and silicates, talc, titaniumdioxide, starch and other organic fillers such as wood flower, andcarbon black. In one embodiment, the filler is carbon black or modifiedcarbon black.

A specific example includes a semi-reinforcing grade carbon blackpresent at a level of from 10 to 150 phr of the composition, morepreferably from 30 to 120 phr. Useful grades of carbon black asdescribed in RUBBER T ECHNOLOGY 59-85 (1995) range from N110 to N990.More desirably, embodiments of the carbon black useful in, for example,tire treads are N229, N351, N339, N220, N234 and N110 provided in ASTM(D3037, D1510, and D3765). Embodiments of the carbon black useful in,for example, sidewalls in tires, are N330, N351, N550, N650, N660, andN762. Embodiments of the carbon black useful in, for example,innerliners or innertubes are N550, N650, N660, N762, N990, and Regal 85(Cabot Corporation, Alpharetta, Ga.) and the like.

The filler may also be a modified clay or be combined with a modifiedclay, such as an exfoliated clay. The layered filler may comprise alayered clay pre-treated with organic molecules.

Layered clays include at least one silicate.

In certain embodiments, the silicate may comprise at least one“smectite” or “smectite-type clay” referring to the general class ofclay minerals with expanding crystal lattices. For example, this mayinclude the dioctahedral smectites which consist of montmorillonite,beidellite, and nontronite, and the trioctahedral smectites, whichincludes saponite, hectorite, and sauconite. Also encompassed aresmectite-clays prepared synthetically, e.g., by hydrothermal processesas disclosed in U.S. Pat. Nos. 3,252,757, 3,586,468, 3,666,407,3,671,190, 3,844,978, 3,844,979, 3,852,405, and 3,855,147.

In yet other embodiments, the at least one silicate may comprise naturalor synthetic phyllosilicates, such as montmorillonite, nontronite,beidellite, bentonite, volkonskoite, laponite, hectorite, saponite,sauconite, magadite, kenyaite, stevensite and the like, as well asvermiculite, halloysite, aluminate oxides, hydrotalcite, and the like.Combinations of any of the previous embodiments are also contemplated.

The layered clay may be intercalated and exfoliated by treatment withorganic molecules such as swelling or exfoliating agents or additivescapable of undergoing ion exchange reactions with the cations present atthe interlayer surfaces of the layered silicate. Suitable exfoliatingadditives include cationic surfactants such as ammonium, alkylamines oralkylammonium (primary, secondary, tertiary and quaternary), phosphoniumor sulfonium derivatives of aliphatic, aromatic or arylaliphatic amines,phosphines and sulfides.

For example, amine compounds (or the corresponding ammonium ion) arethose with the structure R²R³R⁴N, wherein R², R³, and R⁴ are C₁ to C₃₀alkyls or alkenes in one embodiment, C₁ to C₂₀ alkyls or alkenes inanother embodiment, which may be the same or different. In oneembodiment, the exfoliating agent is a so-called long chain tertiaryamine, wherein at least R² is a C₁₄ to C₂₀ alkyl or alkene.

In other embodiments, a class of exfoliating additives include thosewhich can be covalently bonded to the interlayer surfaces. These includepolysilanes of the structure —Si(R⁵)₂R⁶ where R⁵ is the same ordifferent at each occurrence and is selected from alkyl, alkoxy oroxysilane and R⁶ is an organic radical compatible with the matrixpolymer of the composite.

Other suitable exfoliating additives include protonated amino acids andsalts thereof containing 2-30 carbon atoms such as 12-aminododecanoicacid, epsilon-caprolactam and like materials. Suitable swelling agentsand processes for intercalating layered silicates are disclosed in U.S.Pat. Nos. 4,472,538, 4,810,734, and 4,889,885 and WO92/02582.

In an embodiment, the exfoliating additive or additives are capable ofreacting with the halogen sites of the halogenated elastomer to formcomplexes which help exfoliate the clay. In certain embodiments, theadditives include all primary, secondary and tertiary amines andphosphines; alkyl and aryl sulfides and thiols; and their polyfunctionalversions. Desirable additives include: long-chain tertiary amines suchas N,N-dimethyl-octadecylamine, N,N-dioctadecyl-methylamine, so calleddihydrogenated tallowalkyl-methylamine and the like, andamine-terminated polytetrahydrofuran; long-chain thiol and thiosulfatecompounds like hexamethylene sodium thiosulfate.

The exfoliating additive such as described herein is present in thecomposition in an amount to achieve optimal air retention as measured bythe permeability testing described herein. For example, the additive maybe present from 0.1 to 40 phr in one embodiment, and from 0.2 to 20 phrin yet another embodiment, and from 0.3 to 10 phr in yet anotherembodiment.

The exfoliating additive may be added to the composition at any stage;for example, the additive may be added to the elastomer, followed byaddition of the layered filler, or may be added to a combination of atleast one elastomer and at least one layered filler; or the additive maybe first blended with the layered filler, followed by addition of theelastomer in yet another embodiment.

In certain embodiments, treatment with the swelling agents describedabove results in intercalation or exfoliation of the layered plateletsas a consequence of a reduction of the ionic forces holding the layerstogether and introduction of molecules between layers which serve tospace the layers at distances of greater than 4 Å, alternatively greaterthan 9 Å. This separation allows the layered silicate to more readilysorb polymerizable monomer material and polymeric material between thelayers and facilitates further delamination of the layers when theintercalate is shear mixed with matrix polymer material to provide auniform dispersion of the exfoliated layers within the polymer matrix.

In certain embodiments, the layered filler comprises alkyl ammoniumsalts-intercalated clay. Commercial products are available as Cloisitesproduced by Southern Clay Products, Inc. (Gunsalas, Tex.). For example,Cloisite Na⁺, Cloisite 30B, Cloisite 10A, Cloisite 25A, Cloisite 93A,Cloisite 20A, Cloisite 15A, and Cloisite 6A. They are also available asSOMASIF and LUCENTITE clays produced by CO-OP Chemical Co., LTD. (Tokyo,Japan). For example, SOMASIF™ MAE, SOMASIF™ MEE, SOMASIF™ MPE, SOMASIF™MTE, SOMASIF™ ME-100, LUCENTITE™ SPN, and LUCENTITE (SWN).

In certain embodiments, the layered filler generally comprise particlescontaining a plurality of silicate platelets having a thickness of 8-12Å tightly bound together at interlayer spacings of 4 Å or less, andcontain exchangeable cations such as Na⁺, Ca⁺², K⁺ or Mg⁺² present atthe interlayer surfaces.

More recently, modifying agents also include polymer chains withfunctionalized units. For example, suitable modifying agents maycomprise at least one polymer chain E comprising a carbon chain lengthof from C₂₅ to C₅₀₀, wherein the polymer chain also comprises anammonium-functionalized group described by the following group pendantto the polymer chain E:

wherein each R, R¹ and R² are the same or different and independentlyselected from hydrogen, C₁ to C₂₆ alkyl, alkenes or aryls, substitutedC₁ to C₂₆ alkyls, alkenes or aryls, C₁ to C₂₆ aliphatic alcohols orethers, C₁ to C₂₆ carboxylic acids, nitriles, ethoxylated amines,acrylates and esters; and wherein X is a counterion of ammonium such asBr⁻, Cl⁻ or PF₆ ⁻.

The modifying agent may also comprise at least one additional agentcapable of undergoing ion exchange reactions with the cations present atthe interlayer surfaces of the layered filler.

In other embodiments, the polymer chain may comprise a carbon chainlength of from C₃₀ to C₄₀₀, preferably C₃₀ to C₃₀₀, and even morepreferably C₃₀ to C₂₀₀.

In an embodiment, the polymer chain comprises isobutylene derived unitswith the ammonium-functionalized group as described above. In anotherembodiment, the polymer chain may consist essentially ofpoly(isobutylene) with the ammonium-functionalized group as describedabove. In yet another embodiment, the modifying agent may comprise atleast one end-functionalized polyisobutylene amine.

Processing Aids

A processing oil may be present in blends or compositions of theinvention. The processing oil may be selected from paraffinic oil,aromatic oils, naphthenic oils, and polybutene oils.

Distinctly, the polybutene processing oil is a low molecular weight(less than 15,000 Mn) homopolymer or copolymer of olefin derived unitshaving from 3 to 8 carbon atoms, more preferably 4 to 6 carbon atoms. Inyet another embodiment, the polybutene is a homopolymer or copolymer ofa C₄ raffinate. Such low molecular weight polymers termed “polybutene”polymers is described in, for example, SYNTHETIC LUBRICANTS ANDHIGH-PERFORMANCE FUNCTIONAL FLUIDS, P 357-392 (Rudnick & Shubkin, eds.,Marcel Dekker, 1999) (hereinafter “polybutene processing oil” or“polybutene”). Examples of such a processing oil are the PARAPOL™ seriesof processing oils (ExxonMobil Chemical Company, Houston, Tex.), such asPARAPOL™ 450, 700, 950, 1300, 2400, and 2500. The PARAPOL™ series ofpolybutene processing oils are typically synthetic liquid polybutenes,each individual formulation having a certain molecular weight, allformulations of which can be used in the composition. The molecularweights of the PARAPOL™ oils are from 420 Mn (PARAPOL™ 450) to 2700 Mn(PARAPOL™ 2500). The MWD of the PARAPOL™ oils range from 1.8 to 3,preferably 2 to 2.8. The density (g/ml) of PARAPOL™ processing oilsvaries from about 0.85 (PARAPOL™ 450) to 0.91 (PARAPOL™ 2500). Thebromine number (CG/G) for PARAPOL™ oils ranges from 40 for the 450 Mnprocessing oil, to 8 for the 2700 Mn processing oil.

In another embodiment, the processing aid may comprise polyalphaolefins(PAOs), high purity hydrocarbon fluid compositions (HPFCs) and/or GroupIII basestocks such as those described in WO 2004/014998 at page 16,line 14 to page 24, line 1. Examples of PAOs include oligomers of deceneand co-oligomers of decene and dodecene. Preferred PAOs are availableunder the trade name SuperSyn™ PAO (ExxonMobil Chemical Company,Houston, Tex.).

Curing Agents and Accelerators

The compositions produced in accordance with the present inventiontypically contain other components and additives customarily used inrubber mixes, such as pigments, accelerators, cross-linking and curingmaterials, antioxidants, antiozonants, and fillers. In one embodiment,processing aids (resins) such as naphthenic, aromatic or paraffinicextender oils may be present from 1 to 30 phr. In another embodiment,naphthenic, aliphatic, paraffinic and other aromatic resins and oils aresubstantially absent from the composition. By “substantially absent”, itis meant that naphthenic, aliphatic, paraffinic and other aromaticresins are present, if at all, to an extent no greater than 2 phr in thecomposition.

Generally, polymer compositions, e.g., those used to produce tires, arecrosslinked. It is known that the physical properties, performancecharacteristics, and durability of vulcanized rubber compounds aredirectly related to the number (crosslink density) and type ofcrosslinks formed during the vulcanization reaction. (See, e.g., Helt etal., The Post Vulcanization Stabilization for NR, RUBBER WORLD, P 18-23(1991)). Cross-linking and curing agents include sulfur, zinc oxide, andfatty acids. Peroxide cure systems may also be used. Generally, polymercompositions may be crosslinked by adding curative molecules, forexample sulfur, metal oxides (i.e., zinc oxide), organometalliccompounds, radical initiators, etc. followed by heating. In particular,the following are common curatives that will function in the presentinvention: ZnO, CaO, MgO, Al₂O₃, CrO₃, FeO, Fe₂O₃, and NiO. These metaloxides can be used in conjunction with the corresponding metal stearatecomplex (e.g., Zn(Stearate)₂, Ca(Stearate)₂, Mg(Stearate)₂, andAl(Stearate)₃), or with stearic acid, and either a sulfur compound or analkylperoxide compound. (See also, Formulation Design and CuringCharacteristics of NBR Mixes for Seals, RUBBER WORLD, P 25-30 (1993)).This method may be accelerated and is often used for the vulcanizationof elastomer compositions.

Accelerators include amines, guanidines, thioureas, thiazoles, thiurams,sulfenamides, sulfenimides, thiocarbamates, xanthates, and the like.Acceleration of the cure process may be accomplished by adding to thecomposition an amount of the accelerant. The mechanism for acceleratedvulcanization of natural rubber involves complex interactions betweenthe curative, accelerator, activators and polymers. Ideally, all of theavailable curative is consumed in the formation of effective crosslinkswhich join together two polymer chains and enhance the overall strengthof the polymer matrix. Numerous accelerators are known in the art andinclude, but are not limited to, the following: stearic acid, diphenylguanidine (DPG), tetramethylthiuram disulfide (TMTD),4,4′-dithiodimorpholine (DTDM), tetrabutylthiuram disulfide (TBTD),2,2′-benzothiazyl disulfide (MBTS), hexamethylene-1,6-bisthiosulfatedisodium salt dihydrate, 2-(morpholinothio) benzothiazole (MBS or MOR),compositions of 90% MOR and 10% MBTS (MOR 90),N-tertiarybutyl-2-benzothiazole sulfenamide (TBBS), and N-oxydiethylenethiocarbamyl-N-oxydiethylene sulfonamide (OTOS), zinc 2-ethyl hexanoate(ZEH), N,N′-diethyl thiourea.

In one embodiment of the invention, at least one curing agent is presentfrom 0.2 to 15 phr, and from 0.5 to 10 phr in another embodiment. Curingagents include those components described above that facilitate orinfluence the cure of elastomers, such as metals, accelerators, sulfur,peroxides, and other agents common in the art, and as described above.

Processing

Blends of elastomers may be reactor blends and/or melt mixes. Mixing ofthe components may be carried out by combining the polymer components,filler and the clay in the form of an intercalate in any suitable mixingdevice such as a Banbury™ mixer, Brabender™ mixer or preferably amixer/extruder. Mixing is performed at temperatures in the range from upto the melting point of the elastomer and/or secondary rubber used inthe composition in one embodiment, from 40° C. up to 250° C. in anotherembodiment, and from 100° C. to 200° C. in yet another embodiment, underconditions of shear sufficient to allow the clay intercalate toexfoliate and become uniformly dispersed within the polymer to form thenanocomposite.

Mixing may be performed in a BR Banbury™ internal mixer with, forexample, tangential rotors, or, in a Krupp internal mixer with, forexample, intermeshing rotors, by techniques known in the art. Typically,from 70% to 100% of the elastomer or elastomers is first mixed for 20 to90 seconds, or until the temperature reaches from 40° C. to 60° C. Then,¾ of the filler, and the remaining amount of elastomer, if any, istypically added to the mixer, and mixing continues until the temperaturereaches from 90 to 150° C. Next, the remaining filler is added, as wellas the processing oil, and mixing continues until the temperaturereaches from 140 to 190° C. The finished mixture is then sheeted out onan open mill and allowed to cool, for example, to from 60° C. to 100° C.when the curatives are added. Curatives may be added on the open mill,or in a second pass in the internal mixer.

Mixing with the clays is performed by techniques known to those skilledin the art, wherein the clay is added to the polymer at the same time asthe carbon black in one embodiment. The polybutene processing oil istypically added later in the mixing cycle after the carbon black andclay have achieved adequate dispersion in the elastomeric matrix.

The cured compositions of the invention can include various elastomersand fillers with the polybutene processing oil. The compositions of theinvention typically include isobutylene-based elastomers such ashalogenated poly(isobutylene-co-p-methylstyrene), butyl rubber, orhalogenated star-branched butyl rubber (HSBB) either alone, or somecombination with one another, with the polybutene processing oil beingpresent from 5 to 30 phr in one embodiment.

In one embodiment, the composition is halogenatedpoly(isobutylene-co-p-methylstyrene) from 60 to 100 phr that may includenatural rubber from 3 to 40 phr, and polybutene processing oil presentfrom 3 to 30 phr, a filler such as a carbon black from 20 to 100 phr,and an exfoliating clay from 0.5 to 20 phr in one embodiment, and from 2to 15 phr in another embodiment. The cure agents such as phenolicresins, sulfur, stearic acid, and zinc oxide, may be present from 0.1 to10 phr.

In another embodiment, the composition may be a halogenatedpoly(isobutylene-co-p-methylstyrene) from 20 to 100 phr in oneembodiment, and from 60 to 98 phr in another embodiment, and polybuteneprocessing oil present from 3 to 30 phr, a filler such as a carbon blackfrom 20 to 100 phr, and an exfoliating clay from 0.5 to 20 phr in oneembodiment, and from 2 to 15 phr in another embodiment. The cure agentssuch as phenolic resins, sulfur, stearic acid, and zinc oxide, may bepresent from 0.1 to 10 phr.

In yet another embodiment, the composition may be a halogenatedpoly(isobutylene-co-p-methylstyrene) from 70 to 97 phr in oneembodiment, and from 50 to 70 phr in another embodiment, and polybuteneprocessing oil present from 3 to 30 phr, a filler such as a carbon blackfrom 20 to 100 phr, and an exfoliating clay from 0.5 to 20 phr in oneembodiment, and from 2 to 15 phr in another embodiment. The cure agentssuch as phenolic resins, sulfur, stearic acid, and zinc oxide, may bepresent from 0.1 to 10 phr.

The isobutylene-based elastomer useful in the invention can be blendedwith various other rubbers or plastics as disclosed herein, inparticular thermoplastic resins such as nylons or polyolefins such aspolypropylene or copolymers of polypropylene. These compositions areuseful in air barriers such as bladders, innertubes, tire innerliners,air sleeves (such as in air shocks), diaphragms, as well as otherapplications where high air or oxygen retention is desirable. In oneembodiment, the cured composition has an air (air, oxygen, or nitrogenat 60° C.) permeability of from 1.2×10⁻⁸ to 4×10⁻⁸ cm³-cm/cm²-sec-atm,and from 1.5×10⁻⁸ to 3.5×10⁻⁸ cm³-cm/cm²-sec-atm in another embodiment.

In one embodiment, an air barrier can be made by the method of combiningat least one random copolymer comprising a C₄ to C₇ isomonoolefinderived unit, at least one filler, and polybutene oil having a numberaverage molecular weight greater than 400, and at least one cure agent;and curing the combined components as described above.

INDUSTRIAL APPLICABILITY

The blends of the invention may be extruded, compression molded, blowmolded, injection molded, and laminated into various shaped articlesincluding fibers, films, layers, industrial parts such as automotiveparts, appliance housings, consumer products, packaging, and the like.

In addition, the blends are useful in articles for a variety of tireapplications such as truck tires, bus tires, automobile tires,motorcycle tires, off-road tires, aircraft tires, and the like. Theblends may either serve as a material fabricated into a finished articleor a component of a finished article such as an innerliner for a tire.The article may be selected from air barriers, air membranes, films,layers (microlayers and/or multilayers), innerliners, innertubes,treads, bladders, sidewalls, and the like.

All patents and patent applications, test procedures (such as ASTMmethods), and other documents cited herein are fully incorporated byreference to the extent such disclosure is consistent with thisinvention and for all jurisdictions in which such incorporation ispermitted.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.

While the illustrative embodiments of the invention have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by thoseskilled in the art without departing from the spirit and scope of theinvention. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthherein but rather that the claims be construed as encompassing all thefeatures of patentable novelty which reside in the present invention,including all features which would be treated as equivalents thereof bythose skilled in the art to which the invention pertains.

Test Methods

Cure properties were measured using an ODR 2000 and 3 degree arc, or aMDR 2000 and 0.5 degree arc at the indicated temperature. Test specimenswere cured at the indicated temperature, typically from 150° C. to 160°C., for a time corresponding to t90+appropriate mold lag. When possible,standard ASTM tests were used to determine the cured compound physicalproperties (see Table 1). Stress/strain properties (tensile strength,elongation at break, modulus values, energy to break) were measured atroom temperature using an Instron 4202. Shore A hardness was measured atroom temperature by using a Zwick Duromatic. The error (2σ) in measuring100% Modulus is ±0.11 MPa units; the error (2σ) in measuring elongationis ±13% units.

The values “mh” and “ml” used here and throughout the description referto “maximum torque” and “minimum torque”, respectively. The “MS” valueis the Mooney scorch value, the “ML(1+4)” value is the Mooney viscosityvalue. The error (2σ) in the later measurement is ±0.65 Mooney viscosityunits. The values of “t” are cure times in minutes, and “ts” is scorchtime” in minutes.

Tensile measurements were done at ambient temperature on Instron SeriesIX Automated Materials Testing System 6.03.08. Tensile specimens(dog-bone shaped) width of 0.25 inches (0.62 cm) and a length of 1.0inches (2.5 cm) length (between two tabs) were used. The thickness ofthe specimens varied and was measured manually by Mitutoyo DigimaticIndicator connected to the system computer. The specimens were pulled ata crosshead speed of 20 inches/min. (51 cm/min.) and the stress/straindata was recorded. The average stress/strain value of at least threespecimens is reported. The error (2σ) in tensile measurements is ±0.47MPa units.

Oxygen permeability was measured using a MOCON OxTran Model 2/61operating under the principle of dynamic measurement of oxygen transportthrough a thin film as published by Pasternak et al. in 8 JOURNAL OFPOLYMER SCIENCE: PART A-2, P 467 (1970). The units of measure arecc-mil/m²-day-mmHg. Generally, the method is as follows: flat film orrubber samples are clamped into diffusion cells which are purged ofresidual oxygen using an oxygen free carrier gas. The carrier gas isrouted to a sensor until a stable zero value is established. Pure oxygenor air is then introduced into the outside of the chamber of thediffusion cells. The oxygen diffusing through the film to the insidechamber is conveyed to a sensor which measures the oxygen diffusionrate.

In an embodiment, the invention provides for an article comprising acomposition comprising an effective amount of the at least onehalogenated random copolymer to impart to the article a MOCON (as hereindefined) of 37.5 cc-mil/m²-day-mmHg or lower.

In an embodiment, the invention provides for an article comprising acomposition comprising an effective amount of the at least onehalogenated random copolymer to impart to the article a MOCON (as hereindefined) of 35.0 cc-mil/m²-day-mmHg or lower.

In an embodiment, the invention provides for an article comprising acomposition comprising an effective amount of the at least onehalogenated random copolymer to impart to the article a MOCON (as hereindefined) of 32.5 cc-mil/m²-day-mmHg or lower.

In an embodiment, the invention provides for an article comprising acomposition comprising an effective amount of the at least onehalogenated random copolymer to impart to the article a MOCON (as hereindefined) of 30.0 cc-mil/m²-day-mmHg or lower.

Permeability was tested by the following method. Thin, vulcanized testspecimens from the sample compositions were mounted in diffusion cellsand conditioned in an oil bath at 65° C. The time required for air topermeate through a given specimen is recorded to determine its airpermeability. Test specimens were circular plates with 12.7-cm diameterand 0.38-mm thickness. The error (2σ) in measuring air permeability is±0.245 (×10⁸) units.

Inflation Pressure Retention (IPR) was tested in accordance to ASTMF-1112 by the following method: The tires were mounted on standard rimsand inflated to 240 kPa±3.5 kPa. A T-adapter is connected to the valveallowing a calibrated gauge to be connected to one side and inflationair to be added through the other. The tires are checked for leaks,conditioned for 48 hours @21° C.±3° C. for 48 hours and again checkedfor leaks. The inflation pressure is then recorded over a three monthtime frame. The IPR is reported as the inflation pressure loss permonth.

In an embodiment, the tire may comprise an article comprising acomposition comprising an effective amount of the at least onehalogenated random copolymer to impart to the tire an Inflation PressureRetention (IPR) (as herein defined) of 2.0 or lower.

In an embodiment, the tire may comprise an article comprising acomposition comprising an effective amount of the at least onehalogenated random copolymer to impart to the tire an Inflation PressureRetention (IPR) (as herein defined) of 1.8 or lower.

In an embodiment, the tire may comprise an article comprising acomposition comprising an effective amount of the at least onehalogenated random copolymer to impart to the tire an Inflation PressureRetention (IPR) (as herein defined) of 1.6 or lower.

The Intracarcass Pressure (ICP) is run as follows: The tires are mountedon standard rims and inflated to 240 kPa±3.5 kPa. The tires areconnected to a constant inflation pressure system, which uses acalibrated gauge to maintain the inflation at 240 kPa±3.5 kPa. The tiresare checked for leaks, conditioned for 48 hours @21° C.±3° C. and againchecked for leaks. Typically five calibrated gauges with hypodermicneedles are then inserted into the tire with the tip of the needle seton the carcass cord. The readings are taken until the pressure at thecord interface equilibrates (normally 2 months). The ICP is reported asthe average of the readings.

In an embodiment, the tire may comprise an article comprising acomposition comprising an effective amount of the at least onehalogenated random copolymer to impart to the tire an Intracarcass (ICP)(as herein defined) of 80 or lower.

In an embodiment, the tire may comprise an article comprising acomposition comprising an effective amount of the at least onehalogenated random copolymer to impart to the tire an Intracarcass (ICP)(as herein defined) of 75 or lower.

In an embodiment, the tire may comprise an article comprising acomposition comprising an effective amount of the at least onehalogenated random copolymer to impart to the tire an Intracarcass (ICP)(as herein defined) of 70 or lower.

In an embodiment, the tire may comprise an article comprising acomposition comprising an effective amount of the at least onehalogenated random copolymer to impart to the tire an Intracarcass (ICP)(as herein defined) of 65 or lower.

In an embodiment, the tire may comprise an article comprising acomposition comprising an effective amount of the at least onehalogenated random copolymer to impart to the tire an Intracarcass (ICP)(as herein defined) of 60 or lower.

In an embodiment, the tire may comprise an article comprising acomposition comprising an effective amount of the at least onehalogenated random copolymer to impart to the tire an Intracarcass (ICP)(as herein defined) of 55 or lower.

The Tire Durability Test is run by mounting the tires on reinforcedsteel rims of standard size. The tires are inflated to 240 kPa±3.5 kPausing a 50/50 O₂/N₂ mixture and loaded on the test machine. The tiresare run against a 28.5 cm wheel running at 84.5 km/hr in a room at 21°C.±3° C. The load is set using the 100% load for 207 kPa inflation asfound in The Tire Guide. This normally gives a deflection of 30%. Thetire is run for 1 hour at 50% load followed by 1 hour at 100% load. Theinflation pressure is recorded and the pressure is adjusted to thislevel daily for the test duration.

In an embodiment, the tire may comprise an article comprising acomposition comprising an effective amount of the at least onehalogenated random copolymer to impart to the tire a Tire Durability (asherein defined) of 470 or higher.

In an embodiment, the tire may comprise an article comprising acomposition comprising an effective amount of the at least onehalogenated random copolymer to impart to the tire a Tire Durability (asherein defined) of 500 or higher.

In an embodiment, the tire may comprise an article comprising acomposition comprising an effective amount of the at least onehalogenated random copolymer to impart to the tire a Tire Durability (asherein defined) of 550 or higher.

In an embodiment, the tire may comprise an article comprising acomposition comprising an effective amount of the at least onehalogenated random copolymer to impart to the tire a Tire Durability (asherein defined) of 600 or higher.

FIGS. 1, 2, and 3 show that a tire made with an innerliner comprising anEXXPRO™/NR blend (80% EXXPRO™) affords better performance than the tiremade with an innerliner having a Bromobutyl rubber/NR blend of the sameratio (80% BIIR). The values obtained for the tire with an EXXPRO™innerliner approaches values predicted for a tire having an innerlinermade with a 90/10 Bromobutyl/NR blend. Blending the EXXPRO™ elastomerwith a secondary rubber component, i.e. natural rubber, affords acompound with similar processing properties as the 100% Bromobutylrubber innerliner compound.

TABLE 1 Test Methods Parameter Units Test Mooney Viscosity (polymer) ML1 + 8, 125° C., MU ASTM D1646 Mooney Viscosity (composition) ML 1 + 4,100° C., MU ASTM D1646 MOCON (@ 60° C.) cc-mil/m²-day-mmHg See text Airpermeability (@ 65° C.) cm³-cm/cm²-sec-atm See text Mooney Scorch Timets5, 125° C., minutes ASTM D1646 Oscillating Disk Rheometer (ODR) @ 160°C., ±3°arc Moving Die Rheometer (MDR) ASTM D2084 @ 160° C., ±0.5°arc mldeciNewton.meter mh dNewton.m ts2 minute t50 minute t90 minute PhysicalProperties press cured Tc 90 + 2 min @ 160° C. Hardness Shore A ASTMD2240 Modulus 20%, 100%, 300% MPa ASTM D412 die C Tensile Strength MPaElongation at Break % Energy to Break N/mm (J) Hot Air Aging, 72 hrs. @125° C. ASTM D573 Hardness Shore A Modulus 20%, 100%, 300% MPa TensileStrength MPa Elongation at Break % Energy to Break N/mm (J) DeMattiaFlex mm @ kilocycles ASTM D813 modified

Compositions 1-11 were mixed in a laboratory mixer in two steps using aKrupp GK 1.6-liter internal mixer with intermeshing rotors. Compositions1-11 were press cured.

Compositions 1-4 (Table 3) are comparative controls. Compositions 5-11(Table 3) exemplify the benefits of incorporating blends of isobutylenecopolymers comprising a halomethylstyrene moiety. Compositions 5 thru 11represent copolymers of halogenated poly(isobutylene-co-p-methylstyrene)comprising various amounts of halogenation and amounts ofp-methylstyrene (PMS) (see Table 2).

Compositions 5-6 exemplify the use of EXXPRO™ elastomers having a PMSlevel of 5 wt % relative to the copolymer as a whole. These data showthat the addition of the PMS improves the air barrier qualities comparedto the copolymer alone, compositions 1-4. Compositions 7-9 exemplify theuse of EXXPRO™ elastomers having a PMS level higher than 5 wt % relativeto the copolymer. These data show that the addition of higher amounts ofthe PMS further improves the air barrier qualities compared to thecopolymer alone, compositions 1-4, or to the EXXPRO™ elastomers having aPMS level of 5 wt %, compositions 5-6. Compositions 10-11 exemplify theuse of EXXPRO™ elastomers having a BrPMS level higher than 0.85 mole %(see Table 2). These data show that the addition of higher amounts ofthe BrPMS further improves the air barrier qualities compared to thecopolymer alone, compositions 1-4, or of the EXXPRO™ elastomers havingthe same PMS level and 0.85 mole % BrPMS, composition 7.

Compositions 12-19 were mixed in the laboratory in two steps using aKrupp GK 1.6-liter internal mixer with intermeshing rotors. Compositions12-19 were press cured.

Composition 12 (Table 5) is a comparative control. Compositions 13-19(Table 5) exemplify the use of EXXPRO™ elastomers having various PMSlevels relative to the copolymer as a whole and a filler systemconsisting of carbon black and clay. Overall, the air permeabilityimproves upon addition of an exfoliating clay (Table 6).

TABLE 2 Components and Commercial Sources Component Brief DescriptionCommercial Source Bromobutyl 2222 BrominatedPoly(isobutylene-co-isoprene), ExxonMobil Chemical Mooney Viscosity (1 +8, 125° C.) of from 27-37 Company (Houston, TX) MU Bromobutyl 2255Brominated Poly(isobutylene-co-isoprene), ExxonMobil Chemical MooneyViscosity (1 + 8, 125° C.) of from XX-XX Company (Houston, TX) MU HSBBBrominated star-branched Bromobutyl ExxonMobil Chemical Rubber 6222Company (Houston, TX) Chlorobutyl 1066 ChloronatedPoly(isobutylene-co-isoprene), ExxonMobil Chemical Mooney Viscosity (1 +8, 125° C.) of from XX-XX Company (Houston, TX) MU EXXPRO ™ 89-1 5 wt %PMS, 0.75 mol % BrPMS, Mooney ExxonMobil Chemical viscosity of 35 ± 5 MU(1 + 8, 125° C.) Company (Houston, TX) EXXPRO ™ 89-4 5 wt % PMS, 0.75mol % BrPMS, Mooney ExxonMobil Chemical viscosity of 45 ± 5 MU (1 + 8,125° C.) Company (Houston, TX) EXXPRO ™ 01-4 7.5 wt % PMS, 0.85 mol %BrPMS, Mooney ExxonMobil Chemical viscosity of 45 ± 5 MU (1 + 8, 125°C.) Company (Houston, TX) EXXPRO ™ 01-5 10 wt % PMS, 0.85 mol % BrPMS,Mooney ExxonMobil Chemical viscosity of 45 ± 5 MU (1 + 8, 125° C.)Company (Houston, TX) EXXPRO ™ 96-4 12 wt % PMS, 0.85 mol % BrPMS,Mooney ExxonMobil Chemical viscosity of 45 ± 5 MU (1 + 8, 125° C.)Company (Houston, TX) EXXPRO ™ 02-2 7.5 wt % PMS, 1.75 mol % BrPMS,Mooney ExxonMobil Chemical viscosity of 45 ± 5 MU (1 + 8, 125° C.)Company (Houston, TX) EXXPRO ™ 90-10 7.5 wt % PMS, 1.2 mol % BrPMS,Mooney ExxonMobil Chemical viscosity of 45 ± 5 MU (1 + 8, 125° C.)Company (Houston, TX) N660 Carbon black Sid Richardson Carbon Company(Fort Worth, TX) CALSOL ™ 810 Naphthenic Oil R.E. Carroll, Inc ASTM Type103 (Trenton, NJ) CLOISITE ™ 20A Dimethylditallowammonium chlorideSouthern Clay Products modified montmorillonite clay (Gonzalez, TX)Struktol 40MS Aromatic hydrocarbon resin mixture Struktol Co. of America(Stow, OH) SP-1068 Brominated phenol-formaldehyde resin SchenectadyInternational (Schenectady, NY) Stearic acid Cure agent e.g., C.K. WitcoCorp. (Taft, LA) Sulfur Cure agent e.g., R.E. Carroll (Trenton, NJ) MBTSCure accelerator e.g., R.T. Vanderbilt (Norwalk, CT) Zinc Oxide 911 Cureactivator C.P. Hall (Chicago, IL)

TABLE 3 Components of Comparative and Example Compositions 1-11Compound: 1 2 3 4 5 6 7 8 9 10 11 BIIR 2222 100 BIIR 2255 100 SBB 6222100 CIIR 1066 100 Exxpro MDX 89-1 100 Exxpro MDX 89-4 100 Exxpro MDX01-4 100 Exxpro MDX 01-5 100 Exxpro MDX 96-4 100 Exxpro MDX 90-10 100Exxpro MDX 02-2 100 Carbon Black, N660 60 60 60 60 60 60 60 60 60 60 60SP-1068 4 4 4 4 4 4 4 4 4 4 4 Struktol 40MS 7 7 7 7 7 7 7 7 7 7 7Processing Oil, Calsol 8 8 8 8 8 8 8 8 8 8 8 810 Stearic acid 1 1 1 1 11 1 1 1 1 1 Zinc Oxide, Kadox 911 1 1 1 1 1 1 1 1 1 1 1 Sulfur 0.5 0.50.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 MBTS 1.25 1.25 1.25 1.25 1.25 1.251.25 1.25 1.25 1.25 1.25

TABLE 4 Properties of Comparative and Example Compositions 1-11Compound: 1 2 3 4 5 6 7 8 9 10 11 ODR 2000 @160 C. ml, dN · m 7.9 11.47.1 9.9 8.5 10.3 11.1 10.8 9.8 11.9 12.0 mh, dN · m 26.8 32.5 22.5 21.026.7 35.0 37.4 37.1 26.2 57.8 99.4 ts2, minutes 3.1 2.5 3.6 1.6 4.7 4.13.9 4.1 4.2 3.4 2.6 t50, minutes 5.6 4.8 5.9 2.4 8.0 7.4 7.4 7.5 7.0 6.54.8 t90, minutes 13.5 14.5 10.8 3.5 12.0 10.8 11.1 11.1 11.4 9.3 15.8Viscosity, ML(1 + 4)@100 C. 49.6 61.0 49.1 51.4 54.9 58.2 60.0 59.6 55.961.2 60.2 Scorch @135 C., t5 14.7 11.4 15.0 10.4 19.6 16.5 14.2 18.918.6 14.1 8.7 MOCON 29.4 29.0 29.8 26.7 25.4 25.5 23.8 22.9 22.7 21.721.6 Relative to Cmp 1 1.00 0.99 1.02 0.91 0.86 0.87 0.81 0.78 0.77 0.740.74 Hardness, Shore A 41.5 41.9 42.5 36.5 47.3 49.7 50.5 50.5 50.5 57.170.3 Stress/Strain 20% Modulus, MPa 0.47 0.53 0.53 0.46 0.58 0.65 0.630.62 0.65 0.83 1.21 100% Modulus, MPa 0.91 10.8 0.97 0.79 1.3 1.58 1.621.66 1.73 2.82 80.3 300% Modulus, MPa 2.87 3.68 3.01 2.44 3.81 4.92 5.215.28 4.45 8.35 0 Tensile, MPa 9.4 10.9 8.8 7.7 9.3 10.1 10.3 10.2 9.211.0 12.7 Elongation, % 829 793 817 810 885 793 763 760 839 491 180Energy to break, N/mm 10.5 13.2 10.2 9.2 14.5 15.4 15.9 15.7 13.9 9.34.4 DeMattia Flex Growth Kcycles 1724 1724 1724 1724 1724 1724 1760 17601760 451 51 Crack Length, mm 10.2 12.7 7.9 4.3 7.6 18.4 23.6 20.9 8.5 2525 Adhesion Tear Resistance, N/mm 14.4 16.7 6.3 7.1 0.9 0.8 0.9 0.6 0.79.7 1.7

TABLE 5 Components of Comparative and Example Compositions 12-19Compound: 12 13 14 15 16 17 18 19 BIIR 2222 100 Exxpro MDX 89-1 100Exxpro MDX 89-4 100 Exxpro MDX 01-4 100 Exxpro MDX 01-5 100 Exxpro MDX96-4 100 Exxpro MDX 90-10 100 Exxpro MDX 02-2 100 Carbon Black, N660 5555 55 55 55 55 55 55 Closite 20A 5 5 5 5 5 5 5 5 SP-1068 4 4 4 4 4 4 4 4Struktol 40MS 7 7 7 7 7 7 7 7 Processing Oil, Calsol 810 8 8 8 8 8 8 8 8Stearic acid 1 1 1 1 1 1 1 1 Zinc Oxide, Kadox 911 1 1 1 1 1 1 1 1Sulfur 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 MBTS 1.25 1.25 1.25 1.25 1.251.25 1.25 1.25

TABLE 6 Properties of Comparative and Example Compositions 12-19Compound: 12 13 14 15 16 17 18 19 ODR@160 C. ml, dN · m 7.6 9.6 11.011.8 11.6 9.9 13.2 12.7 mh, dN · m 31.0 27.5 36.1 37.4 37.3 25.7 56.989.8 ts2, minutes 4.1 4.4 4.6 3.8 4.3 4.8 3.3 2.8 t50, minutes 9.4 11.111.6 10.7 11.3 10.2 9.7 7.3 t90, minutes 16.9 19.3 19.3 18.8 19.5 18.315.2 15.9 Viscosity, ML(1 + 4)@100 C. 45.4 51.2 54.9 56.3 56.6 51.9 59.756.6 Scorch @ 135 C., t5, minutes 16.0 5.8 6.6 5.5 5.4 6.1 4.4 4.6 MOCON29.0 29.4 23.4 22.9 22.2 21.4 20.6 20.7 Relative to Cmp 1 0.99 0.97 0.800.78 0.75 0.73 0.70 0.70 Hardness, Shore A 45.9 47.7 50.3 51.1 49.9 50.957.9 68.7 Stress/Strain 20% Modulus, MPa 0.56 0.64 0.71 0.69 0.7 0.720.69 1.17 100% Modulus, MPa 1.14 1.48 1.76 1.73 1.78 1.67 2.91 6.95 300%Modulus, MPa 3.4 4.12 5.1 5.31 5.49 4.27 8.71 0 Tensile, MPa 10.4 9.911.1 11.4 11.2 10.1 11.9 12.7 Elongation, % 775 778 739 701 693 861 476221 Energy to break, N/mm 11.5 12.7 12.8 13.3 13.4 14.4 9.8 5.7 DeMattiaFlex-Growth Kcycles 899 1724 1724 1760 1343 1760 51 51 Crack Length, mm25 11.4 25 22.1 25 9.5 25 25 Adhesion Tear Resistance, N/mm 4.9 4.5 4.66.0 7.2 3.1 8.2 1.3

Compositions 20-24 were mixed in a tire factory using a conventionaltwo-step mixing sequence in internal mixers equipped with tangentialrotors. Masterbatch mixing was completed using a GK400 mixer followed bysheeting out on an extruder with roller die. Finalization was completedin a GK160 mixer and stocks sheeted out on a two-roll mill. A cold-feedpin extruder was used to profile each innerliner compound. Compositions20-23 (Table 7) are comparative controls. Composition 24 (Table 7)exemplifies the benefits of incorporating blends of isobutylenecopolymers comprising a halomethylstyrene moiety. Composition 24exemplifies the use of EXXPRO™ elastomers having a PMS level of 10 wt %relative to the copolymer as a whole. These data show that the additionof the PMS improves the air barrier qualities of the polymer blendscompared to the copolymer alone, compare to compositions 21 and 23.

Furthermore, physical property data (hardness, modulus, tensilestrength, elongation, energy to break) data show that the addition ofthe PMS improves the aging corresponding properties since the %-changefrom original properties (100%) are the lowest of the copolymer blends,compare composition 24 to compositions 21 and 23.

Compositions 20-24 were incorporated into a tire as the innerliners. Allother tire components were factory production materials. P205/60 SR15passenger tires were built using automatic building machines and werepress cured. Tires were tested for inflation pressure retention (IPR),intracarcass pressure (ICP), and durability (Table 9). Methods andequipment used to manufacture the innerliners and tires are well knownin the art. (See, e.g., U.S. Pat. Nos. 6,834,695, 6,832,637, 6,830,722,6,822,027, 6,814,116, 6,805,176, 6,802,922, 6,802,351, 6,799,618,6,796,348, 6,796,347, 6,617,383, 6,564,625, and 6,538,066). Theinvention is not limited to any particular method of manufacture forarticles such as innnerliners or tires. These data show that theaddition of the PMS, composition 24, improves the air barrier qualities(IPR and ICP) and the durability compared to the copolymer blends alone,compositions 21 and 23.

TABLE 7 Components of Comparative and Example Compositions 20-24Compound: 20 21 22 23 24 BIIR 2222 100 80 60 CIIR 1068 80 Exxpro MDX01-5 80 NR, SMR20 — 20 40 20 20 Carbon Black, N660 60 60 60 60 60 Resin,SP1068 4 4 4 4 4 Resin, Struktol 40 MS 7 7 7 7 7 Process oil, Calsol 8108 8 8 8 8 Stearic Acid 1 1 1 1 1 Zinc oxide, Kadox 911 1 1 1 1 1 Sulfur0.5 0.5 0.5 0.5 0.5 MBTS 1.25 1.25 1.25 1.25 1.25

TABLE 8 Properties of Comparative and Example Compositions 20-24Compound: 20 21 22 23 24 MDR @160 C, 0.5° arc ml, dN · m 1.64 1.56 1.491.53 2.12 mh, dN · m 4.75 4.9 5.91 5.08 6.84 ts2, minutes 5.23 5.25 5.183.95 5.67 t50, minutes 3.95 4.67 5.46 3.68 6.02 t90, minutes 18.97 9.3411.31 7.64 9.86 Mooney viscosity, 62.7 57.5 54.4 56.8 75.8 ML(1 + 4)@100C. Mooney Scorch@ 9.48 9.45 7.05 11.8 9.83 135° C., t5, minutes MOCON24.7 39.3 59.8 41.8 34.7 Relative to Cmp 20 0.10 0.16 0.24 0.17 0.14Hardness, Shore A 44 44 45 42 49 Stress/Strain 100% Modulus (MPa) 1.11.0 1.1 0.9 1.6 300% Modulus (MPa) 3.9 3.5 3.9 3.2 5.5 Tensile, Mpa 10.19.5 11.7 10.5 12.3 Elongation, % 771 747 692 800 683 Energy to break,N/mm 11.8 9.2 10.3 10.2 14.1 Adhesion @ 100 C. Tear Resistance, N/mm24.3 26.9 26.9 22.3 28.7 Aged 72 hrs@125° C. Aged Hardness, Shore A 5256 53 59 53 % Change 16% 21% 15% 29% 7% Aged Stress/Strain 100% Modulus(MPa) 2.0 2.1 1.9 2.2 2.6 % Change 43% 50% 41% 57% 38% 300% Modulus(MPa) 5.9 5.5 4.9 5.4 7.5 % Change 33% 37% 21% 41% 27% Tensile, Mpa 7.77.2 5.6 6.1 10.2 % Change −31% −32% −111% −72% −21% Elongation, % 524466 372 376 461 % Change −47% −60% −86% −113% −48% Energy to break, N/mm6.7 5.8 3.1 4.0 8.9 % Change −77% −58% −235% −156% −59%

A P205/60 SR15 passenger tire made with an innerliner made from anEXXPRO™/NR blend (80% EXXPRO™) affords better performance than the tiremade with an innerliner having a Bromobutyl rubber/NR blend of the sameratio (80% BIIR). The values obtained for the tire with an EXXPRO™innerliner approaches values predicted for a tire having an innerlinermade with a 90/10 BIIR/NR blend. Blending the EXXPRO™ elastomer with asecondary rubber component, i.e. natural rubber, affords a compound withsimilar processing properties as the 100% Bromobutyl rubber innerlinercompound.

TABLE 9 Tire IPR, ICP and Durability Data Compound IPR ICP Durability 201.45 52.3 708.2 21 2.00 73.7 469.5 22 2.65 118.7 336.1 23 2.35 81.6 34024 1.80 63 511.6

Compositions 25-30 were mixed in a tire factory using a conventionaltwo-step mixing sequence in internal mixers equipped with tangentialrotors. First step masterbatch mixing was completed using a GK400 mixerfollowed by sheeting out on an extruder with roller die. Second stepfinalization was completed in a GK160 mixer and stocks sheeted out on atwo-roll mill. A cold-feed pin extruder was used to profile eachinnerliner compound. Compositions 25-27 (Table 10) are comparativecontrols. Compositions 28-30 (Table 10) exemplify the benefits ofincorporating blends of isobutylene copolymers comprising ahalomethylstyrene moiety. Compositions 28-30 exemplify the use ofEXXPRO™ elastomers having a PMS level of 10 wt % relative to thecopolymer as a whole. Compositions 25 and 28 do not contain a secondaryelastomer. Compositions 26 and 29 contain 20 phr of natural rubber as asecondary elastomer. Compositions 27 and 30 contain 40 phr of naturalrubber as a secondary elastomer.

Data (Table 11) show that the addition of the PMS generally improves theair barrier qualities of the polymer blends compared to the copolymeralone, compare respective compositions 25 and 28, 26 and 29, and 27 and30.

Physical property data show that the addition of the PMS improves theprocessing properties of the polymer blends compared to the polymeralone. Mooney scorch values have a higher %-increase than do the MDR t50and t90 cure properties, compare respective compositions 25 and 28, 26and 29, and 27 and 30.

Furthermore, physical property data show that the addition of the PMSalong with use of a secondary elastomer improves the processingproperties of the polymer blends compared to the polymer alone. Mooneyscorch values have a higher %-increase than do the MDR ts2 scorch andMDR t50 and t90 cure properties, compare respective compositions 25 and28, 26 and 29, and 27 and 30. Mooney viscosity values of the EXXPRO™/NRblends are lower than for the 100% Bromobutyl rubber innerliner, comparecompositions 29 and 30 to composition 25.

TABLE 10 Components of Comparative and Example Compositions 25-30Compound 25 26 27 28 29 30 BIIR 2222 100 80 60 NR, SMR 20 20 40 20 40Exxpro MDX 01-5 100 80 60 SP1068 4 4 4 4 4 4 Carbon Black, N660 60 60 6060 60 60 Strucktol 40 MS 7 7 7 7 7 7 Processing Oil, TDAE 8 8 8 8 8 8Stearic Acid 1 1 1 1 1 1 Zinc Oxide 1 1 1 1 1 1 Sulfur 0.5 0.5 0.5 0.50.5 0.5 MBTS 1.25 1.25 1.25 1.25 1.25 1.25

TABLE 11 Properties of Comparative and Example Compositions 25-30 100 8060 100 BIIR 80 BIIR 60 BIIR Exxpro Exxpro Exxpro 25 26 27 28 29 30 MDR@160° C., 0.5 arc ml, dN · m 1.71 1.47 1.49 1.57 1.76 1.72 mh, dN · m4.87 5.15 6.02 6.77 6.27 6.61 ts2, minutes 4.38 5.13 5.04 4.53 5.6 5.55t50, minutes 3.51 4.87 5.4 5.04 5.92 6.27 t90, minutes 8.08 9.4 11.038.39 10.46 14.39 Mooney viscosity, 78.2 58.5 54.2 70.1 70.2 63.6 ML(1 +4) @100° C. Mooney scorch @135° C., 7.78 6.52 6.33 13.4 11.63 13.95 t5,minutes MOCON 24.4 37.5 55.8 20.5 32.5 54.3 Air Permeability 2.78 3.055.00 2.46 2.87 3.77 Hardness, Shore A 48 47 47 54 48 51 Stress/Strain100% Modulus, MPa 1.39 1.16 1.17 1.93 1.57 1.47 300% Modulus, MPa 4.693.90 4.16 5.87 5.57 5.22 Tensile, MPa 10.54 10.68 12.37 11.21 11.8313.01 Elongation, % 746.9 777.6 721.3 780.7 715.5 715.8 Energy to break,N/mm 15.95 13.39 12.47 18.17 16.06 15.09 Adhesion @100° C., Tear 13.109.68 10.59 4.42 4.49 6.19 Resistance, N/mm Corresponding Change, % −66.3−53.6 −42.4 Fatigue to Failure, cycles 610,442 324,694 127,864 357,860231,268 87,099 Corresponding Change, % −41.4 −28.8 −31.9 Aged 72 hrs@125° C. Aged Hardness, Shore A 50 51 47 58 53 48 Aged Stress/Strain100% Modulus, MPa 1.96 1.86 1.69 2.96 2.74 1.95 % Change 41% 60% 44% 53%74% 33% 300% Modulus, MPa 6.39 5.53 5.11 8.49 8.09 6.34 % Change 36% 42%23% 45% 45% 12% Tensile, MPa 9.24 8.13 7.12 11.66 10.86 8.98 % Change−12% −24% −42% 4% −8% −31% Elongation, % 593.8 564.2 463.1 534.2 514.4480.0 % Change −21% −17% −36% −31% −28% −33% Energy to break, N/mm 12.118.63 5.50 13.17 11.14 7.81 % Change −8% −35% −56% −28% −30% −48%

Compositions 25-30 were incorporated into a tire as the inner linersusing automated building machines. All other tire components were normalproduction materials. Tires were press cured. Compositions 25-30 wereincorporated into a P205/60 SR15 passenger tire. Tires were tested forinflation pressure retention (IPR) and intracarcass pressure (ICP)(Table 12). These data show that the addition of the PMS, compositions28-30, improves the respective air barrier qualities (IPR) compared tothe copolymer blends alone, compositions 20-22 (Table 9) andcompositions 25-27 (Table 12).

TABLE 12 Tire IPR and ICP Data Compound IPR ICP 25 1.45 57.8 26 2.0076.5 27 2.65 108.8 28 1.32 55.8 29 1.66 78.2 30 2.56 117.4

Tires made with an innerliner comprising the use of EXXPRO™ elastomershaving a PMS level of 10 wt % relative to the copolymer as a wholeaffords better performance than the tires made with an innerliner havinga Bromobutyl rubber innerliner having the lowest measured IPR and ICPvalues.

Tires made with an innerliner comprising the use of EXXPRO™ elastomershaving a PMS level of 10 wt % relative to the copolymer as a whole and asecondary elastomer afford better performance than the tires made withan innerliner having a Bromobutyl rubber/secondary elastomer blend ofthe same ratio. The IPR values obtained for the tire with an 80/20EXXPRO™/NR innerliner, composition 29, is equivalent to the value forthe tire having an innerliner made with a 100% BIIR, composition 25.Blending the EXXPRO™ elastomer with a secondary rubber component, i.e.natural rubber, affords a compound with better processing propertiesthan the 100% Bromobutyl rubber innerliner compound, compare Mooneyviscosity and Mooney scorch values for compositions 25 and 29 and 30(Table 11).

1. A composition comprising: at least one halogenated random copolymerof isobutylene and methylstyrene; wherein the at least one halogenatedrandom copolymer comprises at least 9.0 wt % para-methylstyrene, basedupon the weight of the at least one halogenated random copolymer; and atleast one general purpose rubber; wherein the composition comprises from70 phr to 97 phr of the at least one halogenated random copolymer, from30 phr to 3 phr of the at least one general purpose rubber, and 20 phrto 100 phr of carbon black.
 2. The composition of claim 1, wherein theat least one halogenated random copolymer comprises at least 9.5 wt %para-methylstyrene, based upon the weight of the at least onehalogenated random copolymer.
 3. The composition of claim 1, wherein theat least one halogenated random copolymer is halogenated with chlorineor bromine.
 4. The composition of claim 3, wherein the at least onehalogenated random copolymer comprises from 0.1 to 5 wt % halogen basedupon the total weight of the at least one halogenated random copolymer.5. The composition of claim 1, wherein the at least one general purposerubber comprises natural rubbers (NR), polyisoprene rubber (IR),poly(styrene-co-butadiene) rubber (SBR), polybutadiene rubber (BR),poly(isoprene-co-butadiene) rubber (IBR), styrene-isoprene-butadienerubber (SIBR), ethylene-propylene rubber (EPM), ethylene-propylene-dienerubber (EPDM), or mixtures thereof.
 6. The composition of claim 1,wherein the composition further comprises at least one thermoplasticresin or further comprises a secondary composition comprising at leastone thermoplastic resin.
 7. The composition of claim 1, wherein thecomposition comprises: a) at least one additional filler selected fromcalcium carbonate, clay, mica, silica, silicates, talc, titaniumdioxide, starch, wood flower, or mixtures thereof b) at least one clayselected from montmorillonite, nontronite, beidellite, volkonskoite,laponite, hectorite, saponite, sauconite, magadite, kenyaite,stevensite, vermiculite, halloysite, aluminate oxides, hydrotalcite, ormixtures thereof c) at least one processing oil selected from aromaticoil, naphthenic oil, paraffinic oil, or mixtures thereof d) at least onepolybutene processing aid; e) at least one cure package or wherein thecomposition has undergone at least one process to produce a curedcomposition; or f) any combination of a-e.
 8. The composition of claim7, wherein the at least one clay is treated with a modifying agent.
 9. Aprocess to produce the composition of claim
 1. 10. An article comprisingthe composition of claim
 1. 11. The article of claim 10, wherein thecomposition comprises an effective amount of the at least onehalogenated random copolymer to impart to the article a MOCON (as hereindefined) of 37.5 cc-mil/m²-day-mmHg or lower.
 12. The article of claim11, wherein the article is selected from the group consisting ofinnerliners, bladders, air membranes, innertubes, air barriers, films,layers (microlayers and/or multilayers), treads, and sidewalls.
 13. Aprocess to produce the article of claim 11 or
 12. 14. A tire comprisingthe article of claim
 11. 15. The tire of claim 14, wherein thecomposition comprises an effective amount of the at least onehalogenated random copolymer to impart to the tire an Inflation PressureRetention (IPR) (as herein defined) of 2.0 or lower.
 16. The tire ofclaim 14, wherein the composition comprises an effective amount of theat least one halogenated random copolymer to impart to the tire anIntracarcass Pressure (ICP) (as herein defined) of 80 or lower.
 17. Thetire of any of claim 14, wherein the composition comprises an effectiveamount of the at least one halogenated random copolymer to impart to thetire a Tire Durability (as herein defined) of 470 or higher.
 18. Aprocess to produce the tire of claim
 14. 19. A vehicle comprising thetire of claim
 14. 20. A retailer of the tire of claim 14 or the vehicleof claim
 18. 21. The use of an article made from a compositioncomprising at least one halogenated random copolymer of isobutylene andmethylstyrene; wherein the at least one halogenated random copolymercomprises at least 9.0 wt % para-methylstyrene, based upon the weight ofthe at least one halogenated random copolymer and at least one generalpurpose rubber, wherein the composition comprises from 70 phr to 97 phrof the at least one halogenated random copolymer, from 30 phr to 3 phrof the at least one general purpose rubber, and 20 phr to 100 phr ofcarbon black in a tire having at least one of (a) an effective amount ofthe at least one halogenated random copolymer to impart to the tire anInflation Pressure Retention (IPR) (as herein defined) of 2.0 or lower;(b) an effective amount of the at least one halogenated random copolymerto impart to the tire an Intracarcass Pressure (ICP) (as herein defined)of 80 or lower; and (c) an effective amount of the at least onehalogenated random copolymer to impart to the tire a Tire Durability (asherein defined) of 470 or higher.
 22. The use of claim 21, wherein thecomposition comprises an effective amount of the at least onehalogenated random copolymer to impart to the tire an Inflation PressureRetention (IPR) (as herein defined) of 1.8 or lower.
 23. The use ofclaim 21, wherein the composition comprises an effective amount of theat least one halogenated random copolymer to impart to the tire anIntracarcass Pressure (ICP) (as herein defined) of 75 or lower.
 24. Theuse of claim 21, wherein the composition comprises an effective amountof the at least one halogenated random copolymer to impart to the tire aTire Durability (as herein defined) of 500 or higher.
 25. The use ofclaim 21, wherein the composition comprises from 75 phr to 97 phr of theat least halogenated one random copolymer and from 25 phr to 3 phr ofthe at least one general purpose rubber.
 26. The use of claim 21,wherein the at least one halogenated random copolymer comprises at least9.5 wt % para-methylstyrene, based upon the weight of the at least onehalogenated random copolymer.
 27. The use of claim 21, wherein thecomposition comprises: a) at least one additional filler selected fromcalcium carbonate, clay, mica, silica, silicates, talc, titaniumdioxide, starch, wood flower, or mixtures thereof b) at least one clayselected from montmorillonite, nontronite, beidellite, volkonskoite,laponite, hectorite, saponite, sauconite, magadite, kenyaite,stevensite, vermiculite, halloysite, aluminate oxides, hydrotalcite, ormixtures thereof, optionally, treated with modifying agents; c) at leastone processing oil selected from aromatic oil, naphthenic oil,paraffinic oil, or mixtures thereof; d) at least one polybuteneprocessing aid; e) at least one cure package or wherein the compositionhas undergone at least one process to produce a cured composition; or f)any combination of a-e.
 28. The use of claim 27, wherein the at leastone clay is treated with a modifying agent.
 29. The use of claim 27,wherein the tire has at least two of (a), (b), and (c).
 30. The use ofclaim 27, wherein the tire has (a), (b), and (c).